Curable siloxane compositions

ABSTRACT

There is provided herein a curable polysiloxane composition comprising a reactive polysiloxane having the general structural formula (I): 
                         
as described herein. There is provided a method of making the polysiloxane. In addition, there is provided a curable composition including the polysiloxane.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation application of U.S. patentapplication Ser. No. 15/052,156 filed Feb. 24, 2016, which claimspriority to Provisional U.S. Patent Application No. 62/120,540 filedFeb. 25, 2015, the entire contents of both earlier applications areincorporated by reference herein.

FIELD OF THE INVENTION

The invention is directed to polysiloxanes, more specifically, reactivepolysiloxanes and their use in curable compositions and applicationscontaining the same.

BACKGROUND OF THE INVENTION

Polysiloxanes are well-known materials which have long been used as areactive component to react or crosslink or cure with other materials inorder to form a cured composition containing polysiloxane components.Cured compositions containing polysiloxane components are used in avariety of applications. However, when these polysiloxane components areused, they often experience poor compatibility with the othercomponents, resulting in poor clarity (haze), which is especiallydetrimental when clear compositions are desirable.

While reactive polysiloxanes have been prepared, many containpolysiloxane chains of dimethylsiloxy repeat units which make thepolysiloxane incompatible with other organic polymers or othercomponents in the composition. The polysiloxanes often result in poorpaintability, due to the chains of dimethylsiloxy repeat units. Reactivepolysiloxanes have been prepared with pended groups to improve thecompatibility with other components, such as pendent poly(alkyleneoxide) groups. However, these pendent groups often change the partialmolar volume of the reactive polysiloxane, resulting in a loss ofphysical properties, such as comparative tracking index, tensile,modulus and/or low temperature impact resistance. Therefore, there is aneed for a reactive polysiloxane that improves the capability of thereactive polysiloxanes with other components of the composition, asdetermined for example by haze, without loss of the other physicalproperties.

SUMMARY OF THE INVENTION

In one non-limiting embodiment herein there is provided a polysiloxanehaving the general structural formula (I):

wherein each of R¹, R² and R³ is independently a linear or branchedaliphatic group containing up to about 20 carbon atoms, e.g., from 1 toabout 20 carbon atoms, more specifically from 2 to about 16 carbonatoms, an unsubstituted or substituted aryl group containing from 6 toabout 18 carbon atoms, optionally containing at least one heteroatom,and an alicyclic group containing up to about 20 carbon atoms; each R⁴is independently a divalent alkyl group of from 1 to about 6 carbonatoms, an unsubstituted or substituted aryl group containing up to about18 carbon atoms, an unsubstituted or substituted alicyclic groupcontaining up to about 18 carbon atoms, an unsubstituted or substitutedacyl group containing up to about 18 carbon atoms, an ester groupcontaining up to about 8 carbon atoms, an ether group containing up toabout 8 carbon atoms, or an acyl group containing up to about 8 carbonatoms; each Z is independently selected from a divalent linear, branchedor cyclic alkyl group containing from 2 to 25 carbon atoms, a divalentlinear, branched or cyclic alkenyl group containing from 2 to 25 carbonatoms, and a divalent unsubstituted or substituted aryl group of up toabout 20 carbon atoms; each M is independently hydrogen, a hydroxygroup, an alkenyl group of from 2 to about 12 carbon atoms, an alkynylgroup of from 2 to about 12 carbon atoms, an amino group, an alkoxygroup containing from 1 to about 8 carbon atoms, an alkoxyalkyl groupcontaining from 2 to about 10 carbon atoms, an oximoalkyl groupcontaining up to about 8 carbon atoms, wherein the lower endpoint can be1, 2 or 3, an enoxyalkyl group containing up to about 8 carbon atoms,wherein the lower endpoint can be 1, or 2, an aminoalkyl groupcontaining up to about 8 carbon atoms, wherein the lower endpoint can be1 or 2, a carboxyalkyl group containing up to about 8 carbon atomswherein the lower endpoint can be 1 or 2, an amidoaliphatic groupcontaining up to about 8 carbon atoms wherein the lower endpoint can be1 or 2, an amidoaryl group containing up to about 12 carbon atomswherein the lower endpoint can be 6 or 7, a carbamato alkyl groupcontaining up to about 8 carbon atoms wherein the lower endpoint can be2 or 3, an epoxy group containing at least 2 and up to 8 carbon atoms,an anhydride group containing at least 3 or 4 carbon atoms and up to 12carbon atoms, a carboxyl group containing from 1 up to about 8 carbonatoms, a carbonyl group, an acyl group containing from 1 up to about 8carbon atoms, an amide group, an ionic group, an imine group containingfrom 1 or 2 up to about 8 carbon atoms, an isocyanate group, a nitrilegroup, an (meth)acryl group, an (meth)acrylol group, an alkoxysilylgroup containing from 1 to about 8 carbon atoms, an alkoxyalkylsilylgroup containing from 2 to about 8 carbon atoms, an acyloxysilyl groupcontaining from 1 to about 8 carbon atoms, a hydroxyalkylsilyl groupcontaining from 1 to about 8 carbon atoms or a thiol group; and thesubscript x is an integer of from 1 to 250, the subscript y is from 0 to100, the subscript n′ is an integer greater than 1, and the subscript mis an integer of from to 1 to 5.

In yet another embodiment herein there is provided a curable compositioncomprising (a) a polysiloxane of the general formula (I) as describedabove, where M is an alkenyl or alkynyl group, and (b) a polysiloxane ofthe general formula (II):

wherein each of R¹, R², R³, x and y is as defined above, R⁵ is hydrogen,an alkyl group of from 1 to 4 carbon atoms or phenyl, with the provisothat when y is 0 or 1, R⁵ is hydrogen.

In yet even another embodiment herein there is provided a curablecomposition comprising (a) a polysiloxane of the general formula (I)wherein each of R¹, R², R³, R⁴, Z, x, y, and m is as defined above, andeach M is independently selected from an alkenyl group, an alkynylgroup, an amino group, an alkoxy group, an alkoxyalkyl, an oximoalkyl,an enoxyalkyl, an aminoalkyl, a carboxyalkyl, an amidoalkyl, anamidoaryl, a carbamatoalkyl, an epoxy group, an anhydride group, acarboxyl group, a carbonyl group, an acyl group, an amide group, anionic group, an amide group, an imine group, an isocyanate, nitrile, anacryl group, an acrylol group or a thiol group, wherein these groupshave the ranges of carbon atoms defined elsewhere herein, and n′ isgreater than 1, and (b) an initiator for photo-curing and optionally (c)a further reactive component selected from the group consisting of aphoto curable reactive component, a crosslinker of silane type, afiller, adhesion promoter, solvent, cure promoter, a cure retardant andcombinations thereof.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to reactive polysiloxane compounds. Suchpolysiloxane compounds can be used to make copolymers therefrom, e.g.,polycarbonate-polysiloxane copolymers, or curable compositions withimproved physical and chemical properties. The polysiloxane compoundsand copolymers herein have been found to have a higher degree ofpolymerization which provides for improved physical properties in theresultant polymer composition. Some non-limiting examples of suchimprovements can be any one or more of thermal stability, high heatdistortion temperature, comparative tracking index, flame resistance,refractive index, low temperature impact, flexibility withoutcompromising transparency, low-melt viscosity, oxygen barrier property,UV resistance and adhesion, e.g., improved paintability.

Other than in the working examples or where otherwise indicated, allnumbers expressing amounts of materials, reaction conditions, timedurations, quantified properties of materials, and so forth, stated inthe specification and claims are to be understood as being modified inall instances by the term “about” whether or not the term “about” isused in the expression.

It will be understood that any numerical range recited herein includesall sub-ranges within that range and any combination of the variousendpoints of such ranges or sub-ranges, be it described in the examplesor anywhere else in the specification.

It will also be understood herein that any of the components of theinvention herein as they are described by any specific genus or speciesdetailed in the examples section of the specification, can be used inone embodiment to define an alternative respective definition of anyendpoint of a range elsewhere described in the specification with regardto that component, and can thus, in one non-limiting embodiment, be usedto supplant such a range endpoint, elsewhere described.

It will be further understood that any compound, material or substancewhich is expressly or implicitly disclosed in the specification and/orrecited in a claim as belonging to a group of structurally,compositionally and/or functionally related compounds, materials orsubstances includes individual representatives of the group and allcombinations thereof.

Reference is made to substances, components, or ingredients in existenceat the time just before first contacted, formed in situ, blended, ormixed with one or more other substances, components, or ingredients inaccordance with the present disclosure. A substance, component oringredient identified as a reaction product, resulting mixture, or thelike may gain an identity, property, or character through a chemicalreaction or transformation during the course of contacting, in situformation, blending, or mixing operation if conducted in accordance withthis disclosure with the application of common sense and the ordinaryskill of one in the relevant art (e.g., chemist). The transformation ofchemical reactants or starting materials to chemical products or finalmaterials is a continually evolving process, independent of the speed atwhich it occurs. Accordingly, as such a transformative process is inprogress there may be a mix of starting and final materials, as well asintermediate species that may be, depending on their kinetic lifetime,easy or difficult to detect with current analytical techniques known tothose of ordinary skill in the art.

Reactants and components referred to by chemical name or formula in thespecification or claims hereof, whether referred to in the singular orplural, may be identified as they exist prior to coming into contactwith another substance referred to by chemical name or chemical type(e.g., another reactant or a solvent). Preliminary and/or transitionalchemical changes, transformations, or reactions, if any, that take placein the resulting mixture, solution, or reaction medium may be identifiedas intermediate species, master batches, and the like, and may haveutility distinct from the utility of the reaction product or finalmaterial. Other subsequent changes, transformations, or reactions mayresult from bringing the specified reactants and/or components togetherunder the conditions called for pursuant to this disclosure. In theseother subsequent changes, transformations, or reactions the reactants,ingredients, or the components to be brought together may identify orindicate the reaction product or final material.

In one embodiment herein in general formula (I) as described above (andas used elsewhere herein) each of R¹, R² and R³ are independently alinear or branched aliphatic group containing up to about 20 carbonatoms, more specifically up to about 12 carbon atoms, more specificallyup to about 8 carbon atoms, wherein in one more specific embodiment thelower endpoint of such ranges can be any one of 1, 2, 3, 4 or 5, in someembodiments the branched aliphatic group can be an unsaturated group ofthe aforestated carbon atom lengths, or a branched hydrocarbon radicalof the aforestated carbon atom lengths; an unsubstituted or substitutedaryl group containing from 6 to about 18 carbon atoms, more specificallyfrom about 6 to about 12 carbon atoms, and most specifically from 6 toabout 10 carbon atoms, optionally containing at least one heteroatom,e.g., O, N or S, and in some embodiments the aryl group can be a bridgedcyclic aryl group of the aforestated carbon atom lengths; and analicyclic group containing up to about 20 carbon atoms more specificallyup to about 12 carbon atoms, more specifically up to about 8 carbonatoms, wherein in one more specific embodiment the lower endpoint ofsuch ranges can be any one of 1, 2, 3, 4 or 5.

In a further embodiment, general formula (I) as described above (and asused elsewhere herein) can be defined such that each R⁴ isindependently, a divalent alkyl group of from 1 to about 6 carbon atoms,more specifically from 1 to about 4 carbon atoms and most specificallymethyl or ethyl, and in one non-limiting embodiment from 2 to about 6carbon atoms; an unsubstituted or substituted aryl group containing upto about 18 carbon atoms, more specifically up to about 12 carbon atoms,and most specifically up to about 10 carbon atoms, wherein the lowerendpoint of such ranges can be any one of 6, 7, 8, 9 or 10; an estergroup containing up to about 8 carbon atoms, more specifically up toabout 6 carbon atoms and most specifically up to about 3 carbon atoms,wherein the lower endpoint of such ranges can be any one of 2 or 3; anether group containing up to about 8 carbon atoms, more specifically upto about 6 carbon atoms and most specifically up to about 3 carbonatoms, wherein the lower endpoint of such ranges can be any one of 2 or3; or an acyl group containing up to about 8 carbon atoms, morespecifically up to about 6 carbon atoms and most specifically up toabout 3 carbon atoms, wherein the lower endpoint of such ranges can beany one of 1 or 2.

In another embodiment, general formula (I) as described above (and asused elsewhere herein) can be defined such that each Z is independentlya divalent linear, branched or cyclic alkyl group containing up to 25carbon atoms, more specifically up to about 20 carbon atoms, even morespecifically up to about 16 carbon atoms, and yet even more specificallyup to about 12 carbon atoms, and most specifically up to about 10 carbonatoms, e.g., 8 carbon atoms, wherein in one embodiment such ranges canhave a lower endpoint of any one of 1, 2, 3, 4 or 5; a divalent linear,branched or cyclic alkenyl group containing up to 25 carbon atoms, morespecifically up to about 20 carbon atoms, even more specifically up toabout 16 carbon atoms, and yet even more specifically up to about 12carbon atoms, and most specifically up to about 10 carbon atoms, e.g., 8carbon atoms, wherein in one embodiment such ranges can have a lowerendpoint of any one of 2, 3, 4 or 5, or a divalent unsubstituted orsubstituted aryl group of up to about 20 carbon atoms, more specificallyup to about 18 carbon atoms and most specifically up to about 12 carbonatoms, wherein the lower endpoint of such ranges can in somenon-limiting embodiments be any one of 6, 7, 8, 9 or 10.

In another embodiment in general formula (I) as described above (and asused elsewhere herein) the subscript x is an integer of from 1 to 250,more specifically from about 1 to about 100, even more specifically from1 to about 50, yet even more specifically from 1 to about 25, morespecifically from 1 to about 15 and most specifically from 1 to about10. In one embodiment, the aforementioned ranges for the subscript “x”can have lower endpoints of any one of 2, 3, 4, or 5. In anotherembodiment in general formula (I) as described above (and as usedelsewhere herein) the subscript y is an integer of from 0 to 40, morespecifically from 1 to about 30, even more specifically from 1 to about20, yet even more specifically from 1 to about 10 and most specificallyfrom 1 to about 8, wherein said ranges can in one embodiment, have alower endpoint of any one of 2, 3, 4 or 5. In another embodiment thesubscript m is from 1 to 5, more specifically from 1 to any one of 2, 3or 4.

In one embodiment herein the polysiloxane of general formula (I) asdescribed above, has a degree of polymerization as defined by thesubscript n′ to be greater than 1, more specifically≥2, and mostspecifically≥1.2 which is introduced between the siloxane blocks. Itwill be understood that these ranges of polymerization can in onenon-limiting embodiment have upper endpoints of any one of 4, 5, 8, 10,12, 15, 20, 35, 50, 75, 100, 250, 500, 1000, 2500, 5000 and 10,000. Thisdegree of polymerization which can provide flexibility in selectingphysical properties of a copolymer including the same.

In one non-limiting embodiment, each of R¹ and R² can be an alkyl offrom 1 to 6 carbon atoms, more specifically 1 to 4 carbon atoms, such asthe non-limiting examples of methyl and ethyl, more specifically methyl.In one embodiment each R¹ and R² are methyl. Further in someembodiments, each R³ group can be an aryl group of from 6 to 8 carbonatoms, such as the non-limiting example of phenyl. In one embodiment,each R³ group is phenyl. Further, in a more specific embodiment herein,the subscript x can be from 15 to 30, more specifically from 18 to 26,and in some even more specific embodiments x can be from 19 to 25, suchas the non-limiting examples of 20, 22 and 24. In some embodiments, ycan either be 0 or 4. In a more specific embodiment herein thedefinition of Z can be a divalent alkylene group of from 6 to 10 carbonatoms, more specifically from 7 to 9 carbon atoms, such as thenon-limiting example of wherein Z is a divalent octylene group.

It will be understood herein that in one non-limiting embodiment, anydefinition of any one or more of R¹, R², R³, R⁴, Z, M, x, y, n′ and mcan also have the same definition in any formulae that appear hereinthat contain such variables or subscripts.

As used herein the terminology “hydrocarbon radical” includes acyclichydrocarbon radicals, alicyclic hydrocarbon radicals and aromatichydrocarbon radicals.

As used herein in reference to a hydrocarbon radical, the term“monovalent” means that the radical is capable of forming one covalentbond per radical, the term “divalent” means that the radical is capableof forming two covalent bonds per radical and the term “trivalent” meansthat the radical is capable of forming three covalent bonds per radical.Generally, a monovalent radical can be represented as having beenderived from a saturated hydrocarbon compound by conceptual removal ofone hydrogen atom from the compound, a divalent radical can berepresented as having been derived from a saturated hydrocarbon compoundby conceptual removal of two hydrogen atoms from the compound and atrivalent radical can be represented as having been derived from asaturated hydrocarbon compound by conceptual removal of three hydrogenatoms from the compound. For example, an ethyl radical, that is, a—CH₂CH₃ radical, is a monovalent radical; a dimethylene radical, thatis, a —(CH₂)₂— radical, is a divalent radical and an ethanetriylradical, that is, (—)₂CHCH₂— radical, is a trivalent radical, each ofwhich can be represented as having been derived by conceptual removal ofone or more hydrogen atoms from the saturated hydrocarbon ethane.

As used herein, the terminology “acyclic hydrocarbon radical” means astraight chain or branched hydrocarbon radical, preferably containingfrom 1 to 60 carbon atoms per radical, which may be saturated orunsaturated and which may be optionally substituted or interrupted withone or more atoms or functional groups, such as, for example, carboxyl,cyano, hydroxy, halo and oxy. Suitable monovalent acyclic hydrocarbonradicals may include, for example, alkyl, alkenyl, alkynyl,hydroxyalkyl, cyanoalkyl, carboxyalkyl, alkyloxy, oxaalkyl,alkylcarbonyloxaalkylene, carboxamide and haloalkyl, such as, forexample, methyl, ethyl, sec-butyl, tert-butyl, octyl, decyl, dodecyl,cetyl, stearyl, ethenyl, propenyl, butynyl, hydroxypropyl, cyanoethyl,butoxy, 2,5,8-trioxadecanyl, carboxymethyl, chloromethyl and3,3,3-fluoropropyl.

Suitable divalent acyclic hydrocarbon radicals include, for example,linear or branched alkylene radicals, such as, for example, methylene,dimethylene, trimethylene, decamethylene, ethylethylene,2-methyltrimethylene, 2,2-dimethyltrimethylene and linear or branchedoxalkylene radicals such as, for example, methyleneoxypropylene.

Suitable trivalent acyclic hydrocarbon radicals include, for example,alkanetriyl radicals, such as, for example, 1,1,2-ethanetriyl,1,2,4-butanetriyl, 1,2,8-octanetriyl, 1,2,4-cyclohexanetriyl andoxaalkanetriyl radicals such as, for example, 1,2,6-triyl-4-oxahexane.

As used herein the term “alkyl” means a saturated straight or branchedmonovalent hydrocarbon radical. In a preferred embodiment, monovalentalkyl groups are selected from linear or branched alkyl groupscontaining from 1 to 60 carbons per group, such as, for example, methyl,ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,pentyl, hexyl, heptyl, decyl, dodecyl.

As used herein the term “alkenyl” means a straight or branchedmonovalent terminally unsaturated hydrocarbon radical, preferablycontaining from 2 to 10 carbon atoms per radical, such as, for example,ethenyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl and ethenylphenyl.

As used herein, the terminology “alicyclic hydrocarbon radical” means aradical containing one or more saturated hydrocarbon rings, specificallycontaining from 4 to 12 carbon atoms per ring, per radical which mayoptionally be substituted on one or more of the rings with one or morealkyl radicals, each preferably containing from 2 to 6 carbon atoms peralkyl radical, halo radicals or other functional groups and which, inthe case of a monovalent alicyclic hydrocarbon radical containing two ormore rings, may be fused rings. Suitable monovalent alicyclichydrocarbon radicals include, for example, cyclohexyl and cyclooctyl.Suitable divalent hydrocarbon radicals include, saturated or unsaturateddivalent monocyclic hydrocarbon radicals, such as, for example,1,4-cyclohexylene. Suitable trivalent alicyclic hydrocarbon radicalsinclude, for example, cycloalkanetriyl radicals such as, for example,1-dimethylene-2,4-cyclohexylene,1-methylethylene-3-methyl-3,4-cyclohexylene.

As used herein, the terminology “aromatic hydrocarbon radical” means ahydrocarbon radical containing one or more aromatic rings per radical,which may, optionally, be substituted on the aromatic rings with one ormore alkyl radicals, each preferably containing from 2 to 6 carbon atomsper alkyl radical, halo radicals or other functional groups and which,in the case of a monovalent aromatic hydrocarbon radical containing twoor more rings, may be fused rings. Suitable monovalent aromatichydrocarbon radicals include, for example, phenyl, tolyl,2,4,6-trimethylphenyl, 1,2-isopropylmethylphenyl, 1-pentalenyl,naphthyl, anthryl, eugenol and allylphenol as well as aralkyl radicalssuch as, for example, 2-phenylethyl. Suitable divalent aromatichydrocarbon radicals include, for example, divalent monocyclic arenessuch as, for example, 1,2-phenylene, 1,4-phenylene,4-methyl-1,2-phenylene, phenylmethylene. Suitable trivalent aromatichydrocarbon radicals include, for example, trivalent monocyclic arenessuch as, for example, 1-trimethylene-3,5-phenylene.

In an embodiment, the present invention relates to a curablepolysiloxane composition. The curable polysiloxane composition provideselastomers, sealants, adhesives and coatings for desired properties andapplications.

In one non-limiting embodiment herein the polysiloxane compound of thegeneral formula (I) as described herein can be made by step-growthpolymerization. For example, there is provided in one embodiment amethod which comprises hydrosilylating a hydride-terminatedpolysiloxane, such as a hydride-terminated polysiloxane represented bythe general structural formula (III):

wherein each R¹, R² and R³, x and y are as defined herein, with a dieneor an alkyne. The diene in one embodiment can comprise a diene whichcontains a linear, branched or cyclic alkyl group containing from 2 to25 carbon atoms, or more specifically any of the ranges of carbon atomsprovided herein for the divalent alkyl group of the variable Z.Alternatively, the diene can contain a linear, branched or cyclicalkenyl group of from 2 to 25 carbon atoms, or more specifically any ofthe ranges of carbon atoms provided herein for the divalent alkenylgroup of the variable Z.

This hydrosilylating of formula (III) with diene can be done underconventional hydrosilylation conditions, such as with the use of aprecious metal catalyst, e.g., a platinum catalyst, and in somenon-limiting embodiments can be conducted at a temperature of from 80°C. to about 110° C. and for a period of from about 5 to about 8 hours.

Many types of precious metal catalysts, e.g., platinum catalysts, areknown and such platinum catalysts may be used for the hydrosilylationreaction in the present invention. When optical clarity is required thepreferred platinum catalysts are those platinum compound catalysts thatare soluble in the reaction mixture. The platinum compound can beselected from those having the formula (PtCl₂Olefin) and H(PtCl₃Olefin)as described in U.S. Pat. No. 3,159,601, which is hereby incorporated byreference in its entirety. A further platinum containing material usablein the compositions of the present invention is the cyclopropane complexof platinum chloride described in U.S. Pat. No. 3,159,662 herebyincorporated by reference in its entirety. Further the platinumcontaining material can be a complex formed from chloroplatinic acidwith up to 2 moles per gram of platinum of a member selected from theclass consisting of alcohols, ethers, aldehydes and mixtures of theabove as described in U.S. Pat. No. 3,220,972 hereby incorporated byreference in its entirety. The catalysts most specifically used hereinare described in U.S. Pat. Nos. 3,715,334; 3,775,452; and 3,814,730 toKarstedt the contents of which are incorporated by reference herein intheir entireties. Additional background concerning the art may be foundat J. L. Spier, “Homogeneous Catalysis of Hydrosilation by TransitionMetals, in Advances in Organometallic Chemistry, volume 17, pages 407through 447, F. G. A. Stone and R. West editors, published by theAcademic Press (New York, 1979), the contents of which is incorporatedby reference in its entirety.

In one embodiment the precious metal catalysts that may be used herein,are such as the non-limiting examples of rhodium, ruthenium, palladium,osmium, iridium and platinum catalysts and combinations thereof.

In one embodiment herein the platinum catalyst is in a soluble complexform.

In one other embodiment, the platinum catalyst is selected from thegroup consisting of platinic chloride, chloroplatinic acid,bis(acetylacetonato)platinum, (η⁵-cyclopentadienyl)trialkylplatinum andcombinations thereof.

Persons skilled in the art can easily determine an effective amount ofprecious metal catalyst. The catalyst can be present in a very widerange, but normally a range of from about 0.1 to about 10,000 ppm, morespecifically of from about 1 to about 100 ppm.

The method of hydrosilylating of formula (III) with diene can provide ahydride-terminated polysiloxane represented by the structural formula(IV):

wherein each of R¹, R², R³, Z, x, y and n′ are as defined.

In one embodiment, the method can then further comprise hydrosilylationof the hydride-terminated polysiloxane of formula (IV) with anunsaturated compound of the general formula (V):

where R^(4*) is selected from an alkenyl group containing from 2 to 6carbon atoms, more specifically 2 to 4 carbon atoms, such as an allylgroup or a vinyl group, allyl acyl group containing up to 15 carbonatoms, a vinyl acyl group containing up to 15 carbon atoms, allylcarbonyloxy group of up to 15 carbon atoms, allyl phenyl group of up toabout 18 carbon atoms, vinyl phenyl group of from 8 to about 18 carbonatoms, allyl ether group of up to 8 carbon atoms, vinyl ether group ofup to 8 carbon atoms, wherein one or more of such R^(4*) groups canoptionally contain one or more of a hydroxyl group, an alkoxy group offrom 1 to 4 carbon atoms, a hetero atom such as O, N or S; M is asdefined above for formula (I), and the subscript m is an integer of from1 to 5 and as described herein, and when the subscript m=1, then theaforementioned groups of R^(4*) are terminal groups, and when thesubscript m is >1 then the aforementioned groups of R^(4*) comprise atleast one divalent group and one terminal group, to obtain thepolysiloxane compound of formula (I). Some non-limiting examples of thecompound of the general formula (V) include eugenol, allyl acetate,allyl acetoacetate, allyl alcohol, allyl alcohol propoxylate, allylamine, allyl amine hydrochloride, allyl benzyl ether, allyl butyl ether,allyl butyrate, allyl cyanide, allyl chloroacetate, allyl cyclohexanepropionate, allyl methyl carbamate, allyl methyl carbonate, allylmethylsulfone, 2-allyloxybenzaldehyde, allyloxyethanol,4-allyloxy-2-hydroxybenzophenone, 3-allyloxy-2-hydroxy-1-propanesulfonicacid sodium salt, 3-allyloxy-1,2-propanediol, allyl phenyl ether,allylphosphonic acid, allyl sulfonic acid, allylphosphonic acid salt,allyl sulfonic acid salt, allyl propyl ether, allyl trifluoroacetate,tert-butyl N-allyl carbamate, trimethylolpropane allyl ether, vinylacetate, vinyl benzoate, vinyl alcohol, vinyl amine, vinyl acetoacetate,vinyl 4-tert-butylbenzoate, vinyl chloroformate, vinyl chloroformate,vinyl cinnamate, vinyl decanoate, vinyl neodecanoate, vinylneononanoate, vinyl pivalate, vinyl propionate, vinyl stearate, vinyltrifluoroacetate, vinyl valerate, p-vinyl phenol, o-vinyl phenol,p-allyl phenol, o-allyl phenol, vinyl cyanate, vinyl thiocyanate,styrene, α-methylstyrene, allylphenol, vinylphenylamine,allylphenylamine, monomers of vinylnitro, vinyl acetic, vinylcarboxy,vinylbenzoate, vinylphenylsulfides, allyl(meth)acrylate, isocyanates,thiocyanates and mixtures thereof. Such hydrosilylation can occur at thesame conditions as described above.

In one non-limiting embodiment, instead of hydrosilylation, thepolysiloxane of the general formula (I) can also be prepared by any oneor more of anionic polymerization, free-radical polymerization,ring-opening metathesis polymerization (ROMP), acyclic diene metathesis(ADMET), and coordination polymerization, which polysiloxane of thegeneral formula (I) can also use as structural unit in the copolymerdescribed herein.

In one non-limiting embodiment herein there is provided a method for thepreparation of the reactive polysiloxane of formula (I) which isdepicted by the reaction scheme:

wherein R¹, R², R³, R⁴, R^(4*), M, Z, m, n′, x and y are defined aboveand Z¹ is a chemical bond or a divalent linear, branched or cyclic alkylgroups containing up to 16 carbon atoms.

The hydrosilylation steps in the above reaction scheme can be conductedunder the conditions described above.

In one embodiment herein in the method described for making thepolysiloxane (I) after the hydrosilylation of the compound of formula(IV) with the compound of formula (V), the method can further comprisepurifying the siloxane of the formula (I) from the reaction productmixture. Any conventional method of purification can be used, such asfiltration, extraction, distillation and the like. Some more specificmethods of purifying the reaction product mixture can comprise thin filmevaporation, pre-evaporation, a vapor-liquid separation, a packed bedcolumn distillation, a rotary thin film evaporation and anevaporator-stripper purification.

The polysiloxane compounds of general formula (I) have improvedproperties over that of conventional polysiloxane compounds that areused in polymer compositions, e.g., polycarbonate compositions, such aspolysiloxanes which do not have one or more polymerized alkyl, alkenylor aryl spacers in the molecule. In one non-limiting embodiment thepolysiloxane of general formula (I) can have an improvement over suchother siloxanes in an improvement in at least one of refractive index,temperature of decomposition, high molecular weight, lowerpolydispersity, unimodal distribution and glass transition temperature.

In one embodiment, the polysiloxane of general formula (I) can have oneor more of a refractive index of from 1.40 to about 2.25, morespecifically from about 1.42 to about 1.98; a temperature ofdecomposition of from about 350 to about 520° C. and more specificallyfrom about 375 to about 500° C.; a high molecular weight of from about3.5 to about 12 kDa more specifically from about 4.0 to about 10.0 kDa,said molecular weights being weight average molecular weight; lowerpolydispersity of from about 1.10 to about 3.0, more specifically fromabout 1.20 to about 2.5, and a glass transition temperature of fromabout −60 to about −130. In one embodiment, the weight average molecularweight is determined in accordance with ASTM D5296-11, Standard TestMethod for Molecular Weight Averages and Molecular Weight Distributionof Polystyrene by high Performance Size-Exclusion Chromatography.

In one embodiment herein there is provided a curable compositioncomprising at least one polysiloxane of the general formula (I) asdescribed herein. In one further embodiment, such a curable compositioncomprising at least one polysiloxane of the general formula (I) canfurther comprise a polysiloxane of the general formula (II) as describedherein, and/or a crosslinker or chain extender. In one embodiment, thecrosslinker or chain extender is a silane or siloxane crosslinker orchain extender. In one more specific embodiment, the silane or siloxanecrosslinker or chain extender is selected from an alkoxysilane, analkoxysiloxane, an oximosilane, an oximosiloxane, an enoxysilane, anenoxysiloxane, an aminosilane, a carboxysilane, a carboxysiloxane, analkylamidosilane, an alkylamidosiloxane, an arylamidosilane, anarylamidosiloxane, an alkoxyaminosilane, an alkaryaminosiloxane, analkoxycarbamatosilane, an alkoxycarbamatosiloxane, and combinations oftwo or more thereof.

According to one embodiment, the crosslinker component is chosen fromtetraethylorthosilicate (TEOS); methyltrimethoxysilane (MTMS);vinyltrimethoxysilane; methylvinyldimethoxysilane;dimethyldimethoxysilane; dimethyldiethoxysilane; vinyltriethoxysilane;tetra(n-propyl)orthosilicate; tris(methylethylketoximo)vinylsilane;tris(methylethylketoximo)methylsilane; tris(acetamido)methylsilane;bis(acetamido)dimethylsilane; tris(N-methylacetamido)methylsilane;bis(N-methylacetamido)dimethylsilane;(N-methylacetamido)methyldialkoxysilane; tris(benzamido)methylsilane;tris(propenoxy)methylsilane; alkyldialkoxyamidosilanes;alkylalkoxybisamidosilanes; methylethoxybis(N-methylbenzamido)silane;methylethoxydibenzamidosilane;methyldimethoxy(ethylmethylketoximo)silane;bis(ethylmethylketoximo)methylmethoxysilane;(acetaldoximo)methyldimethoxysilane;(N-methylcarbamato)methyldimethoxysilane; (N-methylcarbamato)ethyldimethoxy silane; (isopropenoxy)methyldimethoxysilane;(isopropenoxy)trimethoxysilane; tris(isopropenoxy)methylsilane;(but-2-en-2-oxy)methyldimethoxysilane;(1-phenylethenoxy)methyldimethoxysilane; 2-((1-carboethoxy)propenoxy)methyldimethoxysilane; bis(N-methylamino)methylmethoxysilane;(N-methylamino)vinyldimethoxysilane; tetrakis(N,N-diethylamino)silane;methyldimethoxy(N-methylamino)silane; methyltris(cyclohexylamino)silane;methyldimethoxy(N-ethylamino)silane;dimethylbis(N,N-dimethylamino)silane;methyldimethoxy(N-isopropylamino)silanedimethylbis(N,N-diethylamino)silane;ethyldimethoxy(N-ethylpropionamido)silane;methyldimethoxy(N-methylacetamido)silane;methyltris(N-methylacetamido)silane;ethyldimethoxy(N-methylacetamido)silane;methyltris(N-methylbenzamido)silane;methylmethoxybis(N-methylacetamido)silane;methyldimethoxy(ε-caprolactamo)silane;trimethoxy(N-methylacetamido)silane;methyldimethoxy(O-ethylacetimidato)silane;methyldimethoxy(O-propylacetimidato)silane;methyldimethoxy(N,N′,N′-trimethylureido)silane;methyldimethoxy(N-allyl-N′,N′-dimethylureido)silane;methyldimethoxy(N-phenyl-N′,N′-dimethylureido)silane;methyldimethoxy(isocyanato)silane; dimethoxydiisocyanatosilane;methyldimethoxy-isothiocyanatosilane;methylmethoxydiisothiocyanatosilane; methyltriacetoxysilane;methylmethoxydiacetoxysilane; methylethoxydiacetoxysilane;methylisopropoxydiacetoxysilane; methyl(n-propoxy)diacetoxysilane;methyldimethoxyacetoxysilane; methyldiethoxyacetoxysilane;methyldiisopropoxyacetoxysilane; methyldi(n-propoxy)acetoxysilane; orthe condensates thereof; or a combination of two or more thereof.

In one non-limiting embodiment, there is provided herein a curablecomposition comprising at least one polysiloxane of the general formula(I) as described herein, and a polysiloxane of the general formula (II)as described herein, wherein each of R¹, R², R³, R⁴, x, y, and m informula (II) is as defined in formula (I) herein, and both M groups informula (I) are alkenyl groups of from 2 to about 12 carbon atoms. Suchas the non-limiting example of where both M groups in formula (I) are analkenyl of from 2 to about 12 carbon atoms. It is embodied herein thatthe M groups in formula (I), when alkenyl, can be the same or differentalkenyl group of from 2 to about 12 carbon atoms. Such curablecompositions as described herein can further comprise at least one of acatalyst, adhesion promoter, filler, cure promoter and solvent asdescribed herein. In one non-limiting embodiment formula (I) can be asdescribed herein wherein each M is a hydroxy group and wherein theadhesion promoter is as described herein.

In one more specific embodiment, the curable composition comprising atleast one polysiloxane of the general formula (I) can further comprise acure catalyst and/or initator. In one embodiment, the cure catalyst isselected from the group consisting of metal, metal chelate, an amine, anacid, a base, and combinations thereof.

In yet one more specific embodiment, the curable composition comprisingat least one polysiloxane of the general formula (I) can furthercomprise an optional component selected from the group consisting of anadhesion promoter; filler and, mixtures thereof. Some non-limitingexamples of adhesion promoter can be such that comprise an amino groupcontaining silane or a mixture of different amino group containingsilanes. The amino group-containing silane adhesion promoter agent is acompound having a group containing a silicon atom bonded to ahydrolyzable group (hereinafter referred to as a hydrolyzable groupattached to the silicon atom) and an amino group. Specific examplesthereof include the same silyl groups with hydrolyzable groups describedabove. Among these groups, the methoxy group and ethoxy group areparticularly suitable. The number of the hydrolyzable groups may be 2 ormore, and particularly suitable are compounds having 3 or morehydrolyzable groups.

Some non-limiting examples of suitable adhesion promoters include,N-(2-aminoethyl)aminopropyltrimethoxysilanegamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane,bis(gamma-trimethoxysilypropyl)amine,N-phenyl-gamma-aminopropyltrimethoxysilane,triaminofunctionaltrimethoxysilane,gamma-aminopropylmethyldimethoxysilane,gamma-aminopropylmethyldiethoxysilane,methacryloxypropyltrimethoxysilane, methylaminopropyltrimethoxysilane,gamma-glycidoxypropylethyldimethoxysilane,gamma-glycidoxypropyltrimethoxysilane,gamma-glycidoxyethyltrimethoxysilane,gamma-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,beta-(3,4-epoxycyclohexyl)ethylmethyl-dimethoxysilane,epoxylimonyltrimethoxysilane, isocyanatopropyltriethoxysilane,isocyanatopropyltrimethoxysilane, isocyanatopropylmethyldimethoxysilane,beta-cyano-ethyl-trimethoxysilane,gamma-acryloxypropyl-trimethoxy-silane,gamma-methacryloxypropyl-methyldimethoxysilane, alpha,omega-bis-(aminoalkyl-diethoxysilyl)-polydimethylsiloxanes (Pn=1-7),alpha, omega-bis-(aminoalkyl-diethoxysilyl)-octa-methyltetrasiloxane,4-amino-3,3,-dimethyl-butyl-tri-methoxysilane, andN-ethyl-3-tri-methoxy-silyl-2-methylpropanamine,3-(diethyl-aminopropyl)-trimethoxysilane combinations of two or morethereof, and the like. Particularly suitable adhesion promoters includebis(alkyltrialkoxysilyl)amines and tris(alkyltrialkoxysilyl)aminesincluding, but not limited to, bis(3-propyltrimethoxysilyl)amine andtris(3-propyltrimethoxysilyl)amine.

Some more specific non-limiting examples of adhesion promoters caninclude those selected from the group consisting ofaminoalkyltrialkoxysilane, aminoalkylalkyldialkoxysilane,bis(alkyl-trialkoxysilyl)amine, tris(alktrialkoxysilyl)amine,tris(alkyltrailkoxysilyl)-cyanurate,tris(alkyltrialkoxysilyl)isocyanurate, and combinations thereof.

The filler can be reinforcing or non-reinforcing fillers or combinationsthereof. In one embodiment the filler is selected from the groupconsisting of fumed silica, precipitated silica, clay, carbon black,calcium carbonates and combinations thereof.

In another more specific embodiment, the curable composition comprisingat least one polysiloxane of the general formula (I) can furthercomprise an optional component selected from the group consisting of UVstabilizer, antioxidant, cure accelerator, thixotropic agent,plasticizer, moisture scavenger, pigment, dye, surfactant, solvent andcombinations thereof.

In one other embodiment herein, there is provided a curable compositioncomprising (a) a polysiloxane of the general formula (I), where each Mis independently selected from an alkenyl group, an alkynyl group, anamino group, an alkoxy group, an alkoxyalkyl, an oximoalkyl, anenoxyalkyl, an aminoalkyl, a carboxyalkyl, an amidoalkyl, an amidoaryl,a carbamatoalkyl, an epoxy group, an anhydride group, a carboxyl group,a carbonyl group, an acyl group, an amide group, an ionic group, anamide group, an azo group, an imine group, an isocyanate, nitrile,nitrate, nitro, nitroso group, an acryl group, an acrylol group or athiol group, x is from 1 to 250, y is from 0 to 100, n′ is greater than1 and m is from to 1 to 5, (b) an initiator for photo-curing andoptionally, (c) a further reactive component selected from the groupconsisting of a photo curable reactive component, a crosslinker ofsilane type, a filler, adhesion promoter, solvent, cure promoter, a cureretardant and combinations thereof.

In one embodiment herein any one of the polysiloxane of the generalformula (I), the copolymer thereof as described herein, the compositionof copolymer and further polymer or the curable composition(s) asdescribed herein can be used to form an article. The article can be anyarticle that would be benefited by the improved physical and/or chemicalproperties described herein. Some technologies that would benefit suchan article include automotive, electronic and medical technologies. Inone embodiment the article can be made by molding, shaping, or formingthe any one of the polysiloxane of the general formula (I), thecopolymer thereof as described herein, or the composition of copolymerand further polymer described herein to obtain the article.

In one embodiment herein there is also provided a cured composition madeby the process of curing any of the curable compositions describedherein. Such curing can be provided by any suitable method describedherein, such as for example, by addition curing, condensation curingand/or ultraviolet light curing. The cured composition can be any one ofa solid, a fluid, a liquid or a gum. Such cured compositions can be usedin any one of an elastomer, a sealant, an adhesive, a coating and acombination thereof.

In one embodiment, the comparative tracking index is measured using ASTMD5288-14, Standard Test Method for Determining Tracking Index ofElectrical Materials Using Various Electrode Materials. In anotherembodiment, the haze is determined in accordance with ASTM D1003-13,Standard Test Method for Haze and Luminous Transmittance. In stillanother embodiment, the physical properties of composition containingthe reactive polysiloxane of the present invention are determined inaccordance with ASTM D638-14, Standard Test Method for TensileProperties of Plastics.

While the invention has been described with reference to certainembodiments, it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing from theessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiments disclosed as the best modecontemplated for carrying out this invention but that the invention willinclude all embodiments falling within the scope of the appended claims.

EXAMPLES Example 1

Synthesis of Hydride End-Capped Hybrid Siloxane Polymer

A 1 L three neck round bottom flask fitted with a reflux condenser,dropping funnel and a mechanical stirrer under nitrogen environment wascharged 50 mL of toluene and 1,7-octadiene (13.35 grams, 0.121 mol). Tothis solution 0.29 gram of Karstedt's catalyst (15 ppm of 2 wt % Pt) wasadded. The whole set-up was kept in an oil bath with reactiontemperature maintained at 70° C. Hydride end-capped siloxane(^(H)MD₃₅M^(H), 350 grams, 0.128 mol, wherein the silicone units ofM^(H) and D contain methyl groups other than the one required H group ineach M^(H)) in a dropping funnel was added drop wise over a period of 1hour. The reaction temperature was subsequently increased to 80° C. andcontinue the reaction until all the 1,7-octadiene gets consumed. Aftercompletion of the hydrosilylation polymerization, unreacted startingmaterials, volatile compounds and the solvent were stripped underreduced pressure. The final product was obtained as a yellow colorliquid in quantitative yield and was decolorized with activated charcoalto yield the desired product as a colorless liquid in quantitativeyield. The chemical structure and composition of the copolymers areinferred through spectral and chromatographic.

wherein x is 35 and n′ is 7.75

Example 2

Synthesis of Vinyl End-Capped Hybrid Siloxane Polymer

A 500 mL three neck round bottom flask fitted with a reflux condenser,dropping funnel and a mechanical stirrer under nitrogen environment wascharged 25 mL of toluene and 1,7-octadiene (7.5 grams, 0.067 mol). Tothis solution 0.14 gram of Karstedt's catalyst (15 ppm of 2 wt % Pt) wasadded. The whole set-up was kept in an oil bath with reactiontemperature maintained at 70° C. Hydride end-capped siloxane(^(H)MD₃₅M^(H), 175 grams, 0.064 mol, wherein the silicone units ofM^(H) and D contain methyl groups other than the one required H group ineach M^(H)) in a dropping funnel was added drop wise over a period of 1hour. The reaction temperature was subsequently increased to 80° C. andthe reaction was continued until all the hydride gets consumed. Aftercompletion of the hydrosilylation polymerization, unreacted startingmaterials, volatile compounds and the solvent were stripped underreduced pressure. The final product was obtained as a yellow colorliquid in quantitative yield and was decolorized with activated charcoalto yield the desired product as a colorless liquid in quantitativeyield. The chemical structure and composition of the copolymers areinferred through spectral and chromatographic.

wherein x is 23.6 and n′ is 8.

Example 3

Synthesis of Methoxysilane End-Capped Hybrid Siloxane Polymer

A 500 mL three neck round bottom flask fitted with a reflux condenser,dropping funnel and a mechanical stirrer under nitrogen environment wascharged 50 mL of toluene and 1,7-octadiene (6.65 grams, 0.061 mol). Tothis solution 0.14 gram of Karstedt's catalyst (15 ppm of 2 wt % Pt) wasadded. The whole set-up was kept in an oil bath with reactiontemperature maintained at 70° C. Hydride end-capped siloxane(^(H)MD₃₅M^(H), 175 grams, 0.064 mol, wherein the silicone units ofM^(H) and D contain methyl groups other than the one required H group ineach M^(H)) in a dropping funnel was added drop wise over a period of 1hour. The reaction temperature was subsequently increased to 80° C. Onceall 1,7-octadiene was consumed, vinyl trimethoxysilane (0.5 gram, 0.003mol) in 25 mL of isopropylalcohol was added and reaction was continueduntil all hydride is consumed. After completion of the hydrosilylationpolymerization, unreacted starting materials, volatile compounds and thesolvent were stripped under reduced pressure. The final product wasobtained as a yellow color liquid in quantitative yield and wasdecolorized with activated charcoal to yield the desired product as acolorless liquid in quantitative yield. The chemical structure andcomposition of the copolymers are inferred through spectral analysis.

wherein x is 18.1 and n′ is 5.75.

Example 4

Synthesis of Methacrylate End-Capped Hybrid Siloxane Polymer

A 500 mL three neck round bottom flask fitted with a reflux condenser,dropping funnel and a mechanical stirrer under nitrogen environment wascharged 50 mL of toluene and 1,7-octadiene (6.65 grams, 0.061 mol). Tothis solution 0.14 gram of Karstedt's catalyst (15 ppm of 2 wt % Pt) wasadded. The whole set-up was kept in an oil bath with reactiontemperature maintained at 70° C. Hydride end-capped siloxane(^(H)MD₃₅M^(H), 175 grams, 0.064 mol, wherein the silicone units ofM^(H) and D contain methyl groups other than the one required H group ineach M^(H)) in a dropping funnel was added drop wise over a period of 1hour. The reaction temperature was subsequently increased to 80° C. Onceall 1,7-octadiene was consumed, allyl methacrylate (0.5 gram, 0.003 mol)in 5 mL of toluene was added and reaction was continued until allhydride is consumed. After completion of the hydrosilylationpolymerization, unreacted starting materials, volatile compounds and thesolvent were stripped under reduced pressure. The final product wasobtained as a yellow color liquid in quantitative yield and wasdecolorized with activated charcoal to yield the desired product as acolorless liquid in quantitative yield. The chemical structure andcomposition of the copolymers are inferred through spectral analysis.

wherein x is 11.2 and n′ is 2.2.

Example 5

Synthesis of Epoxy End-Capped Hybrid Siloxane Polymer

A 500 mL three neck round bottom flask fitted with a reflux condenser,dropping funnel and a mechanical stirrer under nitrogen environment wascharged 50 mL of toluene and 1,7-octadiene (6.65 grams, 0.061 mol). Tothis solution 0.14 gram of Karstedt's catalyst (15 ppm of 2 wt % Pt) wasadded. The whole set-up was kept in an oil bath with reactiontemperature maintained at 70° C. Hydride end-capped siloxane(^(H)MD₃₅M^(H), 175 grams, 0.064 mol, wherein the silicone units ofM^(H) and D contain methyl groups other than the one required H group ineach M^(H)) in a dropping funnel was added drop wise over a period of 1hour. The reaction temperature was subsequently increased to 80° C. Onceall 1,7-octadiene was consumed, allyl glycidyl ether (0.4 gram, 0.003mol) in 5 mL of toluene was added and reaction was continued until allhydride is consumed. After completion of the hydrosilylationpolymerization, unreacted starting materials, volatile compounds and thesolvent were stripped under reduced pressure. The final product wasobtained as a yellow color liquid in quantitative yield and wasdecolorized with activated charcoal to yield the desired product as acolorless liquid in quantitative yield. The chemical structure andcomposition of the copolymers are inferred through spectral analysis.

wherein x is 14 and n′ is 3.65.

Example 6

Synthesis of Anhydride End-Capped Hybrid Siloxane Polymer

A 500 mL three neck round bottom flask fitted with a reflux condenser,dropping funnel and a mechanical stirrer under nitrogen environment wascharged 50 mL of toluene and 1,7-octadiene (6.65 grams, 0.061 mol). Tothis solution 0.14 gram of Karstedt's catalyst (15 ppm of 2 wt % Pt) wasadded. The whole set-up was kept in an oil bath with reactiontemperature maintained at 70° C. Hydride end-capped siloxane(^(H)MD₃₅M^(H), 175 grams, 0.064 mol, wherein the silicone units ofM^(H) and D contain methyl groups other than the one required H group ineach M^(H)) in a dropping funnel was added drop wise over a period of 1hour. The reaction temperature was subsequently increased to 80° C. Onceall 1,7-octadiene was consumed, 5-norbornene-endo-2,3-dicarboxylicanhydride (0.55 gram, 0.003 mol) in 5 mL of toluene was added andreaction was continued until all hydride is consumed. After completionof the hydrosilylation polymerization, unreacted starting materials,volatile compounds and the solvent were stripped under reduced pressure.The final product was obtained as a yellow color liquid in quantitativeyield and was decolorized with activated charcoal to yield the desiredproduct as a colorless liquid in quantitative yield. The chemicalstructure and composition of the copolymers are inferred throughspectral analysis.

wherein x is 17.5 and n′=4.5

Examples 7-17 and Comparative Example 1

Cure Formulations

The synthesized vinyl end-capped hybrid siloxane polymer of example 2and the synthesized hydride end capped hybrid siloxane polymer ofexample 1 was independently mixed in different proportions withcomponent A and component B of commercially available elastomerformulation of Liquid silicone rubber (LSR 2050, Momentive) respectivelyin a blender and were cured by compression molding at 180° C. for 10 minunder pressure to get an elastomeric sheet. The respective sheets wereanalyzed for % transmittance, haze, yellowness index (YI) and %elongation (Table 1).

TABLE 1 Comparative Ex. Ex. Ex. Ex. Ex. Ex. Ex. Example 1 Ex. 7 Ex. 8Ex. 9 10 11 12 13 14 15 Ex. 16 17 LSR2050 100 80 60 80 60 100 100 80 8060 60 60 Component A vinyl 20 40 substituted polysiloxane Example 2 2040 20 20 40 40 40 LSR2050 100 100 100 100 100 95 90 95 90 95 90 80Component B Example 1 5 10 5 10 5 10 20 Total 200 200 200 200 200 200200 200 200 200 200 200 % Transmitance 90.6 90 90.5 89.9 89.7 90.1 90.390.1 90.1 89.4 89.3 88.9 Haze 33 8 5.6 5.02 33.4 38.7 15.4 15.7 17.733.1 8.51 37.7 YI 3.58 4.89 5.45 5.86 5.12 3.58 4.66 5.37 5.48 5.38 6.725.2 % elongation 456 489 459 490 481 523 544 492 464 434 414 404 LSR2050 - Liquid silicone rubber, Momentive Inc.

The invention claimed is:
 1. A curable composition comprising at leastone polysiloxane having the general structural formula (I):

wherein each occurrence of R¹, R² and R³ is independently a linear orbranched aliphatic group containing up to about 20 carbon atoms, anunsubstituted or substituted aryl group containing from about 6 to about18 carbon atoms, optionally containing at least one heteroatom, and analicyclic group containing up to about 20 carbon atoms; each occurrenceof R⁴ is independently a divalent alkyl group of from about 1 to about 6carbon atoms, a divalent unsubstituted or substituted aryl groupcontaining up to about 18 carbon atoms, a divalent unsubstituted orsubstituted alicyclic group containing up to about 18 carbon atoms, adivalent unsubstituted or substituted acyl group containing up to about18 carbon atoms, a divalent ester group containing up to about 8 carbonatoms, or a divalent ether group containing up to about 8 carbon atoms;each occurrence of Z is independently selected from a divalent linear,branched or cyclic alkyl group containing from about 2 to about 25carbon atoms, a divalent linear, branched or cyclic alkenyl groupcontaining from about 2 to about 25 carbon atoms, and a divalentunsubstituted or substituted aryl group of up to about 20 carbon atoms;each occurrence of M is independently a hydroxy group, an alkynyl groupof from about 2 to about 12 carbon atoms, an amino group, an alkoxygroup containing from about 1 to about 8 carbon atoms, an alkoxyalkylgroup containing from about 2 to about 10 carbon atoms, an oximoalkylgroup containing up to about 8 carbon atoms, an enoxyalkyl groupcontaining up to about 8 carbon atoms, an aminoalkyl group containing upto about 8 carbon atoms, a carboxyalkyl group containing up to about 8carbon atoms, an amidoaliphatic group containing up to about 8 carbonatoms, an amidoaryl group containing up to about 12 carbon atoms, acarbamato alkyl group containing up to about 8 carbon atoms, ananhydride group, a carboxyl group containing up to about 8 carbon atoms,a carbonyl group, an acyl group containing up to about 8 carbon atoms,an amide group, an ionic group, an imine group containing up to about 8carbon atoms, an isocyanate group, a nitrile group, an (meth)acrylgroup, an (meth)acrylol group, an alkoxysilyl group, an alkoxyalkylsilylgroup, an acyloxysilyl group, a hydroxyalkylsilyl group or a thiolgroup; the subscript x is an integer of from 1 to 250, the subscript yis an integer from 0 to 100, the subscript n′ is an integer from 2 to10,000, and the subscript m is an integer of from to 1 to 5; and atleast one component selected from the group consisting of: a secondpolysiloxane of the general formula (II):

wherein each of R¹, R² and R³ is independently a linear or branchedaliphatic group containing up to about 20 carbon atoms, an unsubstitutedor substituted aryl group containing from about 6 to about 18 carbonatoms, optionally containing at least one heteroatom, and an alicyclicgroup containing up to about 20 carbon atoms; each R⁴ is independently adivalent alkyl group of from about 1 to about 6 carbon atoms, anunsubstituted or substituted aryl group containing up to about 18 carbonatoms, an unsubstituted or substituted alicyclic group containing up toabout 18 carbon atoms, an unsubstituted or substituted acyl groupcontaining up to about 18 carbon atoms, an ester group containing up toabout 8 carbon atoms, an ether group containing up to about 8 carbonatoms, or an acyl group containing up to about 8 carbon atoms; R⁵ is ahydrogen, alkyl group of from 1 to 4 carbon atoms or phenyl, thesubscript x is an integer of from 1 to 250; and the subscript y is aninteger from 0 to 100, with the proviso that when y is 0 or 1, R⁵ ishydrogen, a crosslinker, and a chain extender.
 2. The curablecomposition of claim 1 wherein the crosslinker is at least one silanecrosslinker, at least one siloxane cross linker, or a combinationthereof.
 3. The curable composition of claim 1 wherein the chainextender is at least one silane chain extender, at least one siloxanechain extender, or a combination thereof.
 4. The curable composition ofclaim 1 further comprising at least one other component selected fromthe group consisting of a cure catalyst, a photo-curing initiator, aphoto-curable reactive component, a photo-cure promoter, a cureretardant, an adhesion promoter, a filler, a UV stabilizer, anantioxidant, a cure accelerator, a thixotropic agent, a plasticizer, amoisture scavenger, a pigment, a dye, a surfactant and a solvent.
 5. Thecurable composition of claim 4 wherein the cure catalyst is at least onecure catalyst selected from the group consisting of a metal, a metalchelate, an amine, an acid and a base.
 6. The curable composition ofclaim 4 wherein the adhesion promoter is at least one an amino groupcontaining silane or a mixture of different amino groups containingsilanes.
 7. The curable composition of claim 4 wherein the adhesionpromoter is at least one adhesion promoter selected from the groupconsisting of aminoalkyltrialkoxysilane, aminoalkylalkyldialkoxysilane,bis(alkyl-trialkoxysilyl)amine, tris(alktrialkoxysilyl)amine,tris(alkyltrailkoxysilyl)-cyanurate andtris(alkyltrialkoxysilyl)isocyanurate.
 8. The curable composition ofclaim 4 wherein the filler is a reinforcing filler, a non-reinforcingfillers or combinations thereof.
 9. The curable composition of claim 4wherein the filler is at least one filler selected from the groupconsisting of fumed silica, precipitated silica, clay, carbon black andcalcium carbonate.
 10. The curable composition of claim 1 wherein informula (I) each M is a hydroxy group, an alkoxysilyl group, analkoxyalkylsilyl group, an acyloxysilyl group or a hydroxyalkylsilylgroup and wherein the crosslinker is at least one selected from thegroup consisting of an alkoxysilane, an alkoxysiloxane, an oximosilane,an oximosiloxane, an enoxysilane, an enoxysiloxane, an aminosilane, acarboxysilane, a carboxysiloxane, an alkylamidosilane, analkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, analkoxyaminosilane, an alkaryaminosiloxane, an alkoxycarbamatosilane andan alkoxycarbamatosiloxane.
 11. The curable composition of claim 10further comprising at least one component selected from the groupconsisting of a catalyst, an adhesion promoter, a filler, a curepromoter and a solvent.
 12. A curable composition comprising: (a) apolysiloxane of the general formula (I):

and (b) a polysiloxane of the general formula (II):

wherein each of R¹, R² and R³ are independently a linear or branchedaliphatic group containing up to about 20 carbon atoms, an unsubstitutedor substituted aryl group containing from about 6 to about 18 carbonatoms, optionally containing at least one heteroatom, and an alicyclicgroup containing up to about 20 carbon atoms; each R⁴ is independently,a divalent alkyl group of from about 1 to about 6 carbon atoms, anunsubstituted or substituted aryl group containing up to about 18 carbonatoms, an ester group containing up to about 8 carbon atoms, an ethergroup containing up to about 8 carbon atoms, or an acyl group containingup to about 8 carbon atoms; R⁵ is a hydrogen, alkyl group of from 1 to 4carbon atoms or phenyl; each Z is independently chosen from a divalentlinear, branched or cyclic alkyl group containing from about 2 to 25carbon atoms, a divalent linear, branched or cyclic alkenyl groupcontaining from about 2 to about 25 carbon atoms, and a divalentunsubstituted or substituted aryl group of up to about 20 carbon atoms;both M groups in formula (I) are alkenyl groups of from about 2 to about12 carbon atoms; and the subscript x is an integer of from 1 to 250, thesubscript y is an integer from 0 to 100, the subscript n′ is an integergreater than or equal to 2, and the subscript m is an integer of from to1 to 5; with the proviso that when y is 0 or 1, R⁵ is hydrogen.
 13. Thecurable composition of claim 12 further comprising at least onecomponent selected from the group consisting of a catalyst, an adhesionpromoter, a filler, a cure promoter and a solvent.
 14. A curablecomposition comprising: (a) at least one polysiloxane of the generalformula (I)

wherein each of R¹, R² and R³ are independently a linear or branchedaliphatic group containing up to about 20 carbon atoms, an unsubstitutedor substituted aryl group containing from about 6 to about 18 carbonatoms, optionally containing at least one heteroatom, and an alicyclicgroup containing up to about 20 carbon atoms; each R⁴ is independently,a divalent alkyl group of from about 1 to about 6 carbon atoms, anunsubstituted or substituted aryl group containing up to about 18 carbonatoms, an ester group containing up to about 8 carbon atoms, an ethergroup containing up to about 8 carbon atoms, or an acyl group containingup to about 8 carbon atoms; each Z is independently chosen from adivalent linear, branched or cyclic alkyl group containing from about 2to about 25 carbon atoms, a divalent linear, branched or cyclic alkenylgroup containing from about 2 to about 25 carbon atoms, and a divalentunsubstituted or substituted aryl group of up to about 20 carbon atoms;each M is independently chosen from an alkenyl group, an alkynyl group,an amino group, an alkoxy group, an alkoxyalkyl, an oximoalkyl, anenoxyalkyl, an aminoalkyl, a carboxyalkyl, an amidoalkyl, an amidoaryl,a carbamatoalkyl, an epoxy group, an anhydride group, a carboxyl group,a carbonyl group, an acyl group, an amide group, an ionic group, anamide group, an azo group, an imine group, an isocyanate, nitrile,nitrate, nitro, nitroso group, an acryl group, an acrylol group, analkoxysilyl group, an alkoxyalkylsilyl group, an acyloxysilyl group, ahydroxyalkylsilyl group or a thiol group; x is an integer from 1 to 250,y is an integer from 0 to 100, n′ is an integer greater than 1 and m isan integer from to 1 to 5, (b) at least one photo-curing initiator andoptionally, (c) at least one further component selected from the groupconsisting of a photo curable reactive component, a silane crosslinker,a filler, an adhesion promoter, a solvent, a photo-cure promoter and acure retardant.
 15. An elastomer, a sealant, an adhesive, a coating or acombination thereof comprising the curable composition of claim 1,wherein the curable composition is cured.
 16. An elastomer, a sealant,an adhesive, a coating or a combination thereof comprising the curablecomposition of claim 12 wherein the curable composition is cured.
 17. Anelastomer, a sealant, an adhesive, a coating or a combination thereofcomprising the curable composition of claim 14 wherein the curablecomposition is cured.
 18. The curable composition of claim 1 wherein thecrosslinker is at least one selected from the group consisting of analkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, anenoxysilane, an enoxysiloxane, an aminosilane, a carboxysilane, acarboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, anarylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, analkaryaminosiloxane, an alkoxycarbamatosilane and analkoxycarbamatosiloxane.
 19. The curable composition of claim 1 whereinthe chain extender is at least one selected from the group consisting ofan alkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, anenoxysilane, an enoxysiloxane, an aminosilane, a carboxysilane, acarboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, anarylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, analkaryaminosiloxane, an alkoxycarbamatosilane and analkoxycarbamatosiloxane.
 20. The curable composition of claim 1 whereinin formula (I) each M is a hydroxy group, an alkoxysilyl group, analkoxyalkylsilyl group, an acyloxysilyl group or a hydroxyalkylsilylgroup and wherein the chain extender is at least one selected from thegroup consisting of an alkoxysilane, an alkoxysiloxane, an oximosilane,an oximosiloxane, an enoxysilane, an enoxysiloxane, an aminosilane, acarboxysilane, a carboxysiloxane, an alkylamidosilane, analkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, analkoxyaminosilane, an alkaryaminosiloxane, an alkoxycarbamatosilane andan alkoxycarbamatosiloxane.
 21. The curable composition of claim 20further comprising at least one component selected from the groupconsisting of a catalyst, an adhesion promoter, a filler, a curepromoter and a solvent.